Monoesters of phosphonic acids



United States Patent 3,374,294 MONOESTERS 0F PHOSPHONIC ACIDS EmileCherbuliez and Joseph Rabinowitz, Geneva, Switzerland, assignors toHooker Chemical Corporation, Niagara Falls, N.Y., a corporationof NewYork No Drawing. Continuation-impart of application Ser. No. 230,315,Oct. 11, 1962. This application Nov. 24, 1965, Ser. No. 509,650

6 Claims. (Cl. 260-958) This is a continuation-in-part of United Statespatent application Ser. No. 230,315, filed Oct. 11, 1962, now Patent No.3,268,629.

The present invention relates to new phosphonic monoesters and to animproved process for making phosphonic monoesters. According to theinvention, an alcohol is reacted with an anhydride of a phosphonic acidto produce phosphonic monoesters of high purity in very good yields.

As anhydrides of phosphonic acids there are preferably used thosecommonly known as phosphonic oxides. These anhydrides can be prepared byknown methods, as for example, by the action of the dichloride of aphosphonic acid according to the equation:

in which R represents an aliphatic, aromatic orheterocyclic radical,usually of 1 to 18 carbon atoms, most often of 2 to carbon atoms; theseradicals may be substituted, as for example, with a nitro group or ahalogen atom, such as fluorine. The radical R may more especially berepresented by a monocyclic aryl radical, such as the phenyl,halogeno-phenyl, e.g., p-fiuoro-phenyl, p-chlorophenyl, p-bromo-phenylor nitro-phenyl, e.g., pnitrophenyl radical.

As a phosphonating agent, one may also use polyphosphonic acids, thatis, the partial anhydrides of phosphonic acids, which give a lesseryield of ester, but which permit the recovery, in the form of alkalineearth metal phosphonate, of the phosphonic acid which did not react andwhich may thus be used for another charge. The polyphosphonic acids areconsidered to be phosphonic anhydrides.

The polyphosphonic acids are obtained by heating correspondingphosphonic acids at a temperature between about 120 to 200 degreescenti-grade and under vacuum (about 3 to millimeters of mercury) for aperiod of about 48 to 96 hours. The pyrophosphonic acids may also beprepared by the action of a given quantity of Water on correspondingdichlorides.

It is sufficient to mix an equivalent of phosphonic oxide (RPO with 0.5to 3 moles, especially with 1.2 to 3 moles of anhydrous R OH alcohol(excess alcohol) and to heat the mixture for a period of 3 to 48 hoursat temperatures of between 20 and 200 degrees centigrade, preferablybetween 50 and 150 degrees centigrade, and the reaction may also becarried out under vacuum. The mixture becomes homogeneous and thephosphonic monoester is obtained, as exemplified by the followingequation Generally, the phosphonic monoester is separated from themixture in the form of its salt which may be characterized by theformula if H In the above formulas, R has the significance indicatedpreviously, R represents aliphatic radicals such as alkyl,

alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, orbicycloalkyl, araliphatic radicals such as aralkyl, aromatic radicalssuch as aryl, and heterocyclic radicals, M is a metal selected from thegroup consisting of alkali and alkaline earth metals, and n is greaterthan one. These radicals, including those which contain double andtriple bonds, remain intact during the reaction. The straight chainaliphatic radicals usually are of 1 to 18 carbon atoms, preferably from1 to 8 carbon atoms, while the cycloaliphatic radicals are from 3 to 18,preferably from 3 to 12, and bicycloaliphatic radicals are from 6 to 18carbon atoms, preferably from 6 to 12 carbon atoms. The radicals R mayalso carry one or more compatible substituents such as halogen atoms,particularly chlorine or fluorine, free or esterified hydroxyl orcarboxyl groups, carboxamide, nitrile or amino groups, preferablytertiarysubstituted amino groups of nitrogen atoms, for example,aliphatic radicals such as methyl or ethyl groups or aromatic oraraliphatic radicals such as phenyl or benzyl radicals. Thesesubstituents may be found in any compatible position of the indicatedradicals with respect to the OH to be phosphonated.

Thus, this reaction is a general one and applies to various alcoholtypes. If a polyol is treated by a phosphonic oxide, only one functionalOH is phosphonated, whatever the quantity of oxide is used. Among thepolyols are glycerol, glycol, pentaerythritol, neopentyl glycol,1,4-(hydroxymethyl)benzene, sorbitol and trimethylol propane. With thehalogenated alcohols, and particularly with the chlorinated andfiuorinated alcohols, the reaction is carried out quite normally and thehalogen is retained. With the amino alcohols this reaction proceedsquite well when the amino function is tertiary. Despite the fact thatthe phenylphosphonic oxide has a tendency to react with primary andsecondary amines to yield phosphonic amides,

there are obtained phosphonic monoesters of amino alcohols withunreacted primary or secondary amino groups and only a minimalpercentage of phosphonic amide. This amidized group may, if desired, bereadily hydrolyzed in an acid medium when the ester portion isrelatively stable. The phosphonation reaction is also readilyaccomplished and in good yield with unsaturated alcohols having doubleor triple bonds, singly or in multiple. The reaction is more rapid withprimary than with secondary alcohols, thus, heating for a longer timewill be desirable during phosphonation of a secondary alcohol.

A preferred embodiment of this invention is the reaction of an alcoholwith an anhydride of a phosphonic acid in the presence of a tertiarybase, such as tri-lower alkylamine, e.g., triethylamine 0rtrimethylamine or a cyclic tertiary base, such as pyridine. The additionof an equivalent of the said tertiary base is especially advantageous ifthe radical R is the radical of a tertiary aliphatic alcohol or theradical of an alcohol sensitive to acid, such as a terpene alcohol.

If the radical R is the radical of an a-nitrilo alcohol, the nitrilegroup may be hydrolyzed to form an ester of an a-carboxamido alcohol. Ifthe reaction mixture does not contain any water, there may beintermediate formation of a cyclic derivative of the ester, which iseasily hydrolyzed with water to form the monoester of the a-canboxamidoalcohol. With [3-, 'yand e-nitrilo alcohols the monoesters of thenitrilo alcohols are preferably obtained; the hydrolysis to thecarboxamido derivative does not take place.

The monoesters obtained can be isolated as their metal salts. Thealkaline or alkaline earth metal salts of phosphonic monoesters arepractically neutral in aqueous solution (pH about 6) and can bepreserved indefinitely in aqueous solution (at this pH the time ofhalf-hydrolysis in a 0.1 molar aqueous solution of ester at degreesCentigrade is greater than 500 hours); the salts of phos- 3 phonicmonoesters of amino alcohols are alkaline in aqueous solution (pH105-11) and also are stable at this pH.

In order to isolate the alkaline earth metal or alkali metal salts ofthe phosphonic monoester, including the calcium, barium, strontium,sodium, potassium, lithium, aluminum and magnesium salts, one proceedsas follows:

After cooling, the excess alcohol is distilled (when a large excess isused) under vacuum. The residue is taken up by water and neutralized bya hydroxide of an alkaline earth metal to a pH of 8.2 (turning ofPhenolphthalein). (In the case of amino alcohols, it is desirable to addhydroxide sufficient to obtain a pH of about 11.) The phosphonic acidwhich may still be present (formed by hydrolysis of the oxide which maynot have reacted, or formed in the course of the reaction whenpolyphosphonic acid is used) precipitates partially as an alkaline earthmetal salt; it is completely precipitated by the addition of one voluumeof alcohol. This is filtered and the filtrate which contains thealkaline earth metal salt of the phosphonic monoester is evaporated anddried under vacuum. Generally, the product obtained is pure. If not, itis purified by extraction with boiling acetone (which dissolves theimpurities); after cooling, the alkaline earth metal salt of thephosphonic monoester is filtered.

If it is desired to obtain alkali metal salts of these monoesters, thealkaline earth metal salt is dissolved in water and there is added therequired quantity of carbonate of an alkali metal. The precipitate ofthe alkaline earth metal carbonate formed is filtered off and thefiltrate is evaporated to dryness under vacuum. The amorphous residuetreated by acetone is transformed into a crystalline precipitate whichis the alkali metal salt of the monoester. One may adapt the abovemethods to make other salts.

The alkaline earth metal salts of the phosphonic monoesters of superioraliphatic alcohols or of terpene alcohols are generally insoluble inwater or in 50 percent ethyl alcohol. In order to isolate thesemonoesters, one proceeds preferably as follows:

(a) After cooling, the reaction mass is taken up by ether andneutralized by triethylamine. The triethylammonium salt of thephosphonic acid is filtered off, whereas the trimethylammonium salt ofthe phosphonic monoester is soluble. The ether and the excess of thetertiary base are distilled, the residue is taken up 'by ether and thealkali earth metal salt of the phosphonic monoester is precipitated :byadding an aqueous solution of the corresponding alkali earth metalhalogenide. The precipitate is washed with water and is purified aspreviously described.

(b) If the reaction is carried out in the presence of a tertiary basesuch as trimethylamine, triethylamine or pyridine, the reaction mixtureis taken up by ether and the phosphonate of the tertiary amine isfiltered off. The ether and the excess of the tertiary base aredistilled and the residue is taken up by water. The alkaline earth metalsalt of the phosphonic monoester is precipitated by adding an aqueoussolution of an alkali earth metal halogenide.

If the free phosphonic monoester crystallizes easily, the reactionmixture is taken up by water and the free phosphonic monoester isprecipitated by adding a strong acid, such as hydrochloric acid (this isthe case, for instance, of mcnthyl phenylphosphonic acid).

This new process of phosphonation of alcohols by phosphonic oxides andpolyphosphonic acids has a number of advantages: it leads straight tomonoesters only, it is simple and directly gives pure products in veryhigh yield, calculated as a percentage of the theoretical value.Moreover, the process is quite general and many of the preparedphosphonic monoesters are new.

The monoesters thus obtained and their salts may be used as additives toliquid fuels, such as gasoline, or as products for impregnating fibersso as U) m ke th proof, pest-resistant or vermin-proof..

The invention is illustrated but not limited by the following examples.All parts are by weight and all temperatures are in degrees centignade,unless otherwise indicated.

Example 1 140 parts (1 equivalent) of phenylphosphonic oxide (C H PO and48 to 64 parts (1.5 to 2 moles) of anhydrous methanol are heated to,100degrees centigrade (bath temperature). After cooling, the excess alcoholis evaporated under vacuum and the residue is taken up with 500 to 800parts of H 0. This solution is neutralized by Ca(OH) (or Ba(OH) if onedesires to obtain a barium salt of the monoester) up to a pH at whichphenolphthalein turns to colored form (about 8.2). Then an equal volumeof alcohol is added and the calcium (or barium) phenylphosphonate thusprecipitated is filtered. The filtrate, evaporated to dryness, yieldsthe monome'thylphenylphosphonate of calcium (or barium) which isgenerally pure initially. If it is not, the dry residue is dissolved inboiling acetone and, after cooling, the calcium or bariummonomethylphenylphosphonate is filtered. The yield in pure product,

is 77 percent of theoretical.

Instead of phenylphosphonic oxide, other aryl phosphonic oxides may beemployed to obtain corresponding salts of aryl phosphonic monoesters.

Example 2 The phenylphosphonic monoesters (in the form of their calciumor barium salts) of the alcohols mentioned below have been prepared inthe same manner as described in Example 1.

The monoester of ethanol of the formula:

0 OM CqII5] O C 2H5 Yield=84 percent The monoester of propanol of theformula:

Yield=90 percent The monoester of isopropanol of the formula:

Yield==56 percent The monoester of butanol of the formula:

0 OM o am-i o orr zorricmor-ra Yield= percent The monoester ofisobutanol of the formula:

Yield=60 percent The monoester of amyl alcohol of the formula:

Yield=7l percent In all the above formulas M is Ca or Ba Example 3 Theesters described in Examples 1 and 2 were also obtained with the aid ofpolyphenylphosphonic acid (n-Z) as the phosphonating agent, in thefollowing manner:-

Yield=84 percent In a flask connected to a water-jet pump and immersedin an oil bath, 140 parts (1 mole) of phenylphosphonic acid are heatedgradually to 200 degrees centigrade (bath temperature) and are kept forabout 48 hours to 72 hours at that temperature and under vacuum. Thistreatment produces a polyphenylphosphonic acid with a degree ofcondensation of about 2, which can be verified by the loss of weight ofthe flask or by acidimetric titration (the titratable acidity betweenthe respective colorings of methyl orange and phenolphthalein greatlydiminishes). After cooling, 1.5 to 2.0 moles of alcohol are introducedinto the flask, with the'operation being continued in the mannerdescribed in Example 1. There is obtained a phenylphosphonic monoesterin the form of its barium or calcium salt, described under Examples 1and 2, with yields of 51 percent for the methyl monoester, 44 percentfor the ethyl monoester, 33 percent for the propyl monoester, 22 percentfor the isopropyl monoester, 40 percent for the butyl monoester, 27percent for the isobutyl ester and 22 percent for the amyl ester. Theseyields are clearly below those obtained with .the oxides (Examples 1 and2) but as in the Examples 1 and 2; one may recover all thephenylphosphonic acid which is not transformed into an ester, in theform of an alkaline earth metal salt.

Example 4 140 parts (1 equivalent) of phenylphosphonic oxide and 84 to112 parts (1.5 to 2.0 moles) of propargyl alcohol are heated to 90degrees Centigrade. One then isolates the monopropargylphenylphosphonateof barium or calcium in the manner already described in Example 1. It isillustrated by the structural formula:

and 120 to 161 parts (1.5 to 2.0 moles) of 2-chloroethanol are heatedfor 16 hours at 120 degrees centigrade (bath temperature). Aftercooling, the excess of chlorohydrin is distilled oil under .vacuum andone isolates the ibarium salt of the mno(2-chloroethyl)phenylphosphonicacid,

0H CaH5P=O oomomol in a yield of 85 percent.

In a similar manner, except for the temperature and duration of heating(which are shown in parenthesis), the phosphonic monoesters ofhalogenated alcohols mentioned below are obtained, with yieldsindicated.

Phenylphosphonic monoester of 3-chloropropanol-1 :(100 degrees'centigrade, 16 hours) of the formula:

/OH CaH5-P=O O CHzCHaCHzCI all) Yield=56 percent Phenylphosphonicmonoester of 3-fiuoropropanol-l degress centigrade, 48 hours) of theformula:

10 Odin-I Yield=40' percent Phenylphosphonic monoester of-2,2,3,3-tetrafluoropropanol-l (100 degrees centigrade, 48 hours) of theformula:

,OCHaCHzCHzF i/ o ns-1 Yield=60 percent All of these are new products.In the above formulas M=Ca or Ba Example 6 parts (1 equivalent) ofphenylphosphonic oxide (C I-I PO and 91 to 124 parts (1.5 to 2.0 moles)of glycol are heated 48 hours at 100 degrees centigrade (bathtemperature). There is isolated the calcium or barium salt of the(2-hydroxyethyl-1)phenylphosphonic acid,

in the manner described in Example 1, with a yield of 60 percent. I

In a similar manner, except as it relates to the temperature for thetetramethyleneglycol, there are prepared the alkaline earth metal saltsof phenylphosphonic monoesters of diols mentioned below with the yieldsindicated:

Phenylphosphonic monoester of propanediol-l,3 of the formula:

(I) OM C6H5-I OCH2CH CHzOH Yield=6'5 percent The phenylphosphonicmonoester of butanediol-1,4 (here the reaction takes place at 50 degreescentigrade, for 4 8 hours) of the formula:

Yield=72 percent Phenylphosphonic monoester of pentanediol-1,5 of theformula:

O OM

OCHzCHzCHaCHzCHgOH Yield-=77 percent In the case of butanediol-1,4(tetramethyleneglycol), the temperature should not exceed 6 0 degreesCentigrade, in order to avoid the formation of tetrahydrofurane in thephosphonation process.

Also, even if there is used a large excess of a phosphonating agent,only one group OH is phosphonated.

All of these esters are new. In the formulas given M=Ca or Ba Example 7140 parts (1 equivalent) of phenylphosphonic oxide and 267 to 336 parts(3 to 4 moles) of dimethylcolamine (dimethylaminoethanol) are heated for3 hours at 120 degrees centigrade. The excess of dimethylcolarnine isdistilled off under vacuum and the residue is dissolved in 800 to 1000parts of water. There is then added an excess of calcium hydroxide insuspension in water with the mixture being agitated for several minutes.After filtering, one volume of alcohol is added to the filtrate tocompletely precipitate the calcium phenylphosphonate still present. Thisis followed by further filtration and evaporation under vacuum. Anamorphous residue is obtained, which, after being treated with boilingacetone, cooled and filtered, yields a precipitate of calciumdimethylaminophenylphosphonate. The formula of this compound is O OCaOOHzCHzN(CH )2 and it was obtained in 50' percent yield.

In treating 1-diethylaminopropanol-2 in the above described manner,there is obtained by evaporation under vacuum an aqueous alcoholicsolution of calcium (l-diethylaminopropyl-2 phenylphosphonate,

CsHs-P OCH-CH3 CH2N(C2H5)2 which is pure. The yield is 30 percent.

Example8 140 parts (1 equivalent) of phenylphosphonic oxide and 152.5(2.5 moles) of colamine are heated at 180 degrees centigrade (bathtemperature) up to the point where the mass becomes homogeneous. Then avacuum is created in the flask, which is kept at this temperatureovernight. After cooling, the reactive mass is dissolved in 800 to 1000parts of water with the addition of an excess of calcium hydroxide. Thismixture is agitated and an equal volume of ethanol is added. The liquidis filtered and evaporated dry under vacuum. The residue is treated withboiling alcohol and yields, after cooling, a precipitate of calcium(Z-aminoethyl)phenylphosphonate,

0 0080.5 ll C6H5P OCHQCHQNHi in 4 0 percent yield.

Example 9 Example One mole of cetylic alcohol and one equivalent ofphenylphosphonic oxide are heated for 48 hours at 110 degreescentigrade. After cooling, the reaction mixture is taken up by ether andfour equivalents of triethylamine are added. The precipitate oftriethylammonium phenylphosphonate is filtered olf, whereas thetriethylammonium salt of the monoester is soluble. The ether and excessof triethylamine are evaporated under reduced pressure and the residueis taken up by ether. This solution, treated with aqueous bariumchloride, yields a gelatinous precipitate which is filtered off, washedwith water and then with acetone and ether, and finally dried in vacuumover P 0 The yield is 50 percent of pure barium cetyl phenylphosphonate:

CflH5 OCHz(CHz)uCHs When cetyl alcohol, used as starting material in theabove example, is replaced by one of the alcohols of the followingformulas: CH (CH CH OH,

CH CH CH OH or CHF (CF CH OH, and when using the described procedure,the following barium phenylphosphonic monoesters are obtained:

One mol of nerol, two moles of triethylamine and one equivalent ofphenylphosphonic oxide are mixed carefully (the reaction is exothermicand it is necessary to cool). After a few minutes the mixture becomeshomogerious. It is then heated at 100 degrees centigrade for 15 hours(with good agitation). After cooling, the reaction mass is taken up byanhydrous ether. The triethylammonium phenylphosphonate is filtered offand the ether and the excess of triethylamine are evaporated underreduced pressure. The oily residue is dissolved in water and the pHbrought to about 5, by adding dilute hydrochloric acid. When an excessof a concentratedaqueous solution of calcium chloride is added to thepreceding solution, voluminous precipitate of the calcium salt of thephenylphosphonic monoester appears. This precipitate, which retains mostof the unreacted terpene alcohol, is washed with water and then withacetone which dissolves most of the retained alcohol. To achieve theelimination of the retained alcohol, the precipitate is finally washedwith ether and then dried in vacuo over P 0 The yield is 30 percent ofpure calcium neryl phenylphosphonate 1e z2 a o.5-

In a similar manner, the calcium salts of the phenylphosphonicmonoesters of geraniol and famesol are obtained in 31 percent yieldeach.

Example 12 Three moles of menthol, 3 moles of pyridine and 3 equivalentsof phenylphosphonic oxide are mixed very carefully until the massliquefies and becomes homogenous. The mixture is then heated for 15hours at -75 degrees centigrade. After cooling, the reaction mixture istaken up by water. This solution is introduced slowly and with agitationin normal hydrochloric acid (3 liters). The precipitate ofmenthylphenylphosphonic acid is filtered olT, Washed with water and thenheated at 60 degrees centigrade, in vacuo, for one night, in order toeliminate any trace of menthol which has been retained by theprecipitate. In this manner, pure menthyl phenylphosphonic acid, C H OP, melting point 91 degrees centigrade, is obtained in an 81 percentyield.

In a similar manner, bornyl phenylphosphonic acid, C H O P, meltingpoint 104-105 degrees centigrade, is prepared from borneol in an 88percent yield.

Example 13 One mole of lactonitrile and one equivalent ofphenylphosphonic oxide are heated at 90 degrees centigrade for 46 hours.After cooling, the reaction mass is taken up by cold water and isquickly neutralized by barium hydroxide to a pH of 8.2 (turning ofphenolphthalein). One volume of cold alcohol is then added to completethe precipitation of the barium phenylphosphonate which is filtered offand discarded. The filtrate is evaporated and the residue is treatedwith acetone, filtered and dried. The dry residue is treated againseveral times with acetone in order to eliminate completely any trace oflactonitrile that would be still present, and dried in vacuo. The yieldof pure barium 2-carbamido-2-ethyl phenylphosphonate is 89 percent.

The a-nitrilo alcohols are transformed, under the described conditions,into the corresponding carboxamidoalkyl phenylphosphonic monoesters,{3-, 'yand 6-nitrilo alcohols yield the corresponding nitriloalkylphenylphosphonic monoesters.

In a similar manner are phosphonated the nitrilo alcohols of thefollowing formulas (yield of the barium salt of the monoester inparenthesis): NC-CH OH percent); NCC(CH OH (64 percent) NCCH CH OH (70percent); NCCH(CH )-CH OH (34 percent); NCCH CH CH OH (58 percent);

(59 percent). The first two nitrilo alcohols yield the coru respondingcarboxamidoalkyl phenylphosphonic monoesters and the other nitriloalcohols (,B-, 'yand 6-nitrilo alcohols) yield the correspondingnitriloalkyl phenylphosphonic monoesters.

Example 14 One mole of anhydrous glycerol and one mole ofphenylphosphonic oxide are heated at 165 degrees centigrade until themass liquefies, and then for 20 hours at 120 degrees centigrade. Thereaction mass treated in the manner described in Example 1, yields crudebarium 10 with barium hydroxide to a pH of 8.2 and diluted with water tofive liters. One volume of alcohol is added and the bariumphenylphosphonate is filtered off. The filtrate is evaporated to drynessunder vacuum, and the residue treated with ether (in order to dissolveany traces of retained tribromoethanol) yields the pure bariumtribromoethyl phenylphosphonate having the following formula:

CBr CH OP(O) (C -H (038 .5) Yield: 70 percent In a similar manner areprepared the phenylphosphonic monoesters of trichloroethanol,trichloroisopropanol and trifiuoroethanol:

CCl CH OP (O) (C H )(OBa Yield: 88 percent CC1 CH[OP(O) (C H )](OB'.5)CH

Yield: 78 percent CF CH OP(O) (C H )(OBao.5) Yield: 81 percent Example16 In a similar manner as described in Examples 1 to 15,p-fiuorophenylphosphonic monoesters are obtained in good yields whenp-fluorophenylphosphonic oxide (a novel oxide) is reacted with thecorresponding alcohol.

Using, for example, as starting alcohols: methanol, tbutanol, t-amylalcohol, propane-1,3-diol, 2-chloro-1- ethanol, n-decanol,2-amino-1-ethanol, Z-dimethylaminol-ethanol, lactonitrile andZ-nitrilo-l-ethanol, the following p-fiuorophenylphosphonic monoestersare obtained:

RP(O)(OM)(OCH3) 70%); 3)3 (53%); (CZHS)(CH3)COP(O)(R)(OM)HOCH2CH2CH2OP(O) (R) (OM) 70%); c1cH cH oP o (R) (OM) (62%);CH3(CH2)8CH2OP(O)(R)(OM) (62%); H2NCH2CH2OP(O)(R) (OM) (53%(CH3)2NCH2CH2OP(O)(R)(OM) (30 H2NCOCH(CH3)OP(O)(R)(OM) (38%);NCCH2CH2OP(O) (R) (OM) (64%).

R represents the p-fiuorophenyl radical (FC H M represents an equivalentof an alkali earth metal and the yield is indicated in parenthesis.p-Fluorophenylphosphonic oxide reacts with all the other alcoholsmentioned in Examples 1 to 15 to yield the correspondingp-fiuorophenylphosphonic monoesters.

The p-fiuorophenylphosphonic oxide is prepared as follows according tothe equation:

/Cl HO\ O O O G e 3 01 HO O HOCH CHOHCH OP(O) (C H (OBa t-bariurna-glyceryl phenylphosphonate HOCH CH[OP(O) (C H (OBau,5) ]CH OH:bar1-urn B-glyceryl phenylphosphonate The determination of the neighboring OHgroups by the method of Malaprade indicates that the product is composedof 51.5 percent of barium ot-glyceryl phenylphosphonate and of 48.5percent of the fl-derivative.

Example 15 Six moles of tri bromoethanol and 4 equivalents ofphenylphosphonic oxide are heated at 90 degrees centigrade for 44 hours.After cooling, the reaction mass 18 taken up by cold alcohol or acetoneand poured immediately into two liters of water. This mixture isneutralized 38 grams (0.216 mole) of p-fluorophenylphosphonic acid and64 grams (0.3 mole) of p-fluorophenylphosphonyl dichloride are heated at200 degrees centigrade for two hours (under light vacuum in order tofacilitate the elimination of the hydrochloric gas evolved during thereaction). The excess of dichloride is distilled under reduced pressure.After cooling, the residue is heated with 400 milliliters of dry benzeneuntil complete dissolution. This solution is left for two days at 5degrees centigrade and the precipitate (p-fiuorophenylphosphonic oxide)filtered off. The filtrate is left again for two days at 5 degreescentigrade and a second amount of p-fluorophenylphosphonic oxide isfiltered oif. The operation is repeated until no further precipitationoccurs (after concentration of the solution to 200 milliliters). Theprecipitates are washed with benzene and dried in vacuo at 60 degreescentigrade. In this manner, 60 grams of pure p-fluorophenylphosphonicoxide, melting point 109-111 degrees centigrade, are obtained (yield 88percent).

(C H O FP) .--Calculated: F, 12.0 percent; P, 19.6 percent; equivalentweight, 158.1. Found: F, 12.4 percent; P, 19.3 percent; equivalentweight, 160.

1 1 1 2 What is claimed is: 3. A compound in accordance with claim 1 ofthe 1. A compound selected from the group consisting of formulacompounds represented by the formulas O M OH OH 5 R3P=o Rr-Pio and R;P=O031 OR! ORI wherein R and R are each as defined in claim 1.

4. A compound according to claim 2, wherein R is wherein R is selectedfrom the group consisting of 10 p-fiuorophenyl. halogeno-phenyl andnitro-phenyl, R is selected from 5, A compound according to claim 3,wherein R is phenyl, halogeno-phenyl and nitrophenyl, R isbicycloselected from the group consisting of phenyl and palkyl of 6 to18 carbon atoms, and M is selected from fluorop'henyl.

the group consisting of alkali metals and alkaline earth 6. Bornylp-fiuorophenylphosphonate. metals. 15

2. A compound in accordance with claim 1 of the References Cited formulaUNITED STATES PATENTS 2,329,707 9/1943 Farrington et al. 260-958 X 202,360,302 10/1944 Etzler et al. 260958 X RP 0 2,792,374 5/1957 Bradleyet al. 260--958 X 0R1 CHARLES B. PARKER, Primary Examiner.

wherein R and R are each as defined in claim 1. RAYMOND: AssistantExaminer- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo. 3,374,294 March 19, 1968 Emile Cherbuliez et al.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 3, line 19, "voluume" should read volume line 44,"trimethylaxpmonium" should read trlethylammonium Column 5, lines 43 to46, the bottom portion of the formula reading ocn cu=cn should read OCH-CH=CH Column 6, line 17, "degress" should read degrees Column 7, lines18 and 19, "dimethylaminophenylphosphonate" should readdimethylaminoethylphenylphosphonate lines 30 to 35, that portion of theformula reading CH-'CH O H-CH Should read CH N H N C H line 66, "of",second occurrence, should read by Column 11, lines 4 to 9 the right-hand formula should appear as shown below:

Signed and sealed this 2nd day of September 1969.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF COMPOUNDSREPRESENTED BY THE FORMULAS